,r 46040 9 A7 B7 經濟部智慧財產局員工消f合作社印製 五、發明說明（1 ) 本發明有關三氟化硼與硫酸領域，更特別的是有關三 氟化硼水合物之流出物轉化成三氟化硼與硫酸。 三氟化硼是一種氣體，於工業中特別使用彼作爲大量 反應之觸媒：聚合作用、酯化作用、烷基化作用與異構化 作用。工業上I該三氟化硼經使用後以一種氫氧化鈉水溶 液處理，然後廢棄所形成由含氟與溴衍生物組成之流出物 〇 爲避免此等含氟與溴廢棄物I在最終反應時收集使用 後之三氟化硼，其呈B.F 3水合物溶液形式，一方面使 B F3與水接觸，另一方面以水淸洗使用b f3催化反應中 形成之有機化合物製得該水合物溶液（參見例如專利E P 3 6 4 8 1 5 )。 因爲存在原有有機雜質之故，該三氟化硼水合物溶液 通常或多或少呈有色狀態，此現象可能係其內容物包含數 P pm至數千p pm有機碳所致（工業値·•自約1 0至 1 0 0 0 p p m )。 專利US 5，536，484描述一種用以升級呈 對應工業規格四氫硼酸水溶液形式之B F 3水合物的方法= 然而，需要使用一種活性碳作去色處理之最終步驟，其中 該活性碳於使用後必定受到破壞。 其他升級工業B F 3水合物之方法敘述於E P 3 6 4 8 1 5，主要包括以硫酸、發煙硫酸或S〇3處理 該工業水合物使該三氟化硼再生。很不幸地，該硫酸使此 操作呈黃至黑色，因此在其未經純化處理之前不適於使用 (諳先閱讀背面之注意事項再填寫本頁) 裝 ---—訂丨 II---丨—^ 未紙張尺度適用中國a家標準（CNS)A4規格（210 X 297公釐） -4 - 46040 § A7 B7 經濟部智慧財產局貝工消费合作社印製 五、發明說明（2 ), r 46040 9 A7 B7 Employees of the Intellectual Property Bureau of the Ministry of Economic Affairs, printed by cooperatives V. Description of the invention (1) The present invention relates to the field of boron trifluoride and sulfuric acid, and more particularly to the conversion of boron trifluoride hydrate effluent Form boron trifluoride and sulfuric acid. Boron trifluoride is a kind of gas, which is especially used in the industry as a catalyst for a large number of reactions: polymerization, esterification, alkylation and isomerization. Industrially, the boron trifluoride is treated with an aqueous sodium hydroxide solution after use, and then the effluent composed of fluorine-containing and bromine derivatives is discarded. To avoid these fluorine-containing and bromine wastes, I The used boron trifluoride was collected in the form of a BF 3 hydrate solution. On the one hand, B F3 was contacted with water, and on the other hand, the organic compound formed in the b f3 catalytic reaction was washed with water to prepare the hydrate solution. (See for example patent EP 3 6 4 8 1 5). Because of the existence of original organic impurities, the boron trifluoride hydrate solution is usually more or less colored. This phenomenon may be caused by the content of organic carbon containing several pm to thousands of pm (industrial 値 · • from about 10 to 100 ppm). Patent US 5,536,484 describes a method for upgrading BF 3 hydrate in the form of an aqueous solution of tetrahydroboric acid corresponding to the industrial specifications = However, it is necessary to use an activated carbon as the final step of decolorization treatment, wherein the activated carbon is used in Must be destroyed later. Other methods for upgrading industrial B F 3 hydrate are described in EP 3 6 4 8 1 5 and mainly include treating the industrial hydrate with sulfuric acid, oleum or S03 to regenerate the boron trifluoride. Unfortunately, the sulfuric acid makes this operation yellow to black, so it is not suitable for use until it has been purified (谙 Please read the precautions on the back before filling this page). ----- Order 丨 II --- 丨— ^ The paper size is in accordance with China A Standard (CNS) A4 (210 X 297 mm) -4-46040 § A7 B7 Printed by Shellfish Consumer Cooperative of Intellectual Property Bureau of the Ministry of Economic Affairs 5. Description of invention (2)
Q 另一方面，欲作爲催化應用之工業B F3不能存在有機 物質與二氧化碳·>該工業產物必須每公斤B F3包含少於 1 0毫克有機碳與少於5毫克C〇2。 現在已發現一種可以自工業B F3水合物與發煙硫酸製 備對應工業規格之三氟化硼與硫酸之方法。此方法特殊優 點係其不會產生廢棄物，不需要使用活性碳。 本發明方法包括下列連續步驟： (a )使發煙硫酸與工業B F3水合物反應， (b )收集釋出之氣態工業B F3，及 (c )以過氧化氫處理步驟（a )之硫酸副產物，並 以空氣處理之。 B F3水合物係通式B Fs · 2 H2〇之二水合物，並 且根據本發明方法，以稱爲工業B F 3水合物之含水組成物 形式使用_。此組成物主要包括一種水與二水合物及上述雜 質之混合物。通常將氣態B F 3吸收於水中，然後將彼用於 各種聚合方法（聚-烯屬烴類、石油樹脂等），並以 水淸洗自該聚合作用製得之聚合物，如此製得該組成物。 其亦可自水解經使用B F 3複合物，諸如例如 BFa^O (C2H5) 2 產生 ° 該欲處理之工業B 合物的B F3含量限制極廣泛 ’但是就容易升級而言，使用濃度介於35與65·3% 之工業8 1^3水合物爲佳，介於4 7與6 5.3%爲更佳（ 以每1 0 0克含水組成物之B F3重量表示）。除非另有所 本紙張尺度適用中困0家標準（CNS)A4規格（210 X 297公釐} -5- — — III — .-----* I I I ί 訂-—I —I I I — *吹 (請先閱讀背面之注意事項再填窝本頁) 4 6〇4〇 9 A7 B7 五、發明說明（3 ) 述，否則本文所示之百分比均爲重量百分比。 亦可以每莫耳BF 3中水之莫耳數X (相對於無水之分 子’即未複合水之分子）表示該工業B F3水合物之BF3 含量。因此，上述相當於X値之B F3重量含量範圍係廣義 範圍介於約0與5，較佳範圍介於約〇與2 . 2。因此， 可以BF3· 2H2〇 + xH2〇定義存在工業BF3水合物 中之水與二水合物混合物。 若情況需要，如專利E P 3 6 4 8 1 5所述，達 成此B F3含量之方法係於真空下去除水，濃縮稀釋B 水合物：自該塔底部排出之經濃縮水合物包含微量重有機 物質（有機碳含量：自約10至lOOOppm)。 本發明方法所使用之發煙硫酸係一種硫酸酐S 〇3於硫 酸中之溶液，該溶液之S 〇3含量介於5與6 5% ’介於 1 0與6 5爲佳。此含量亦可以溶解1莫耳S 〇3之 H2 S 〇4.莫耳數y表示。因此上述之S 〇3重量含量範圍 對應之y値介於0 . 44與15 . 5，介於〇 . 44與 7 . 4爲佳。該發煙硫酸可以表示爲：S〇3 + y Η ξ S 0 4 ° 由工業BF3水合物與發煙硫酸（步驟製備三氟化 硼相當於下列反應： (BF) · 2H2〇 + xH2〇) + (2 + x)[S〇3 + yH2S〇4]— BF3 + (2 + x. + 2y + xy)HiSOt ⑴ (靖先閱讀背面之注意事項再填寫本頁) 裝 ----訂 *------1 -^' 經濟部智慧財產局員工消霣合作杜印製 本紙張尺度適用中a a家標準（CNS)A4規格<210 X 297公釐） -6 - A7 B7 五、發明說明（4 ) 其中，X與y如上述。 於本發明方法步驟（a )中反應之發煙硫酸與工業 B F 3水合物含量之選擇方式係發煙硫酸（以S 〇3莫耳數 表示）數量除以工業水合物（以無水或複合水之莫耳總數 表示）介於0 . 5與1 . 5，接近1爲佳》 步驟（a )之反應通常係於介於7 5與1 1 0°C溫度 進行，介於100與110 °C爲佳。 根據本發明方法步驟（b)，該反應釋出且經收集之 氣態三氟化硼通常位於_反應頂部，其不包含氮或二氧化碳 。其具有市售產物之所有特徵，而且可經處理以便以一般 方式供應，例如經由壓縮作用。 本發明方法步驟（c )中，以過氧化氬處理步驟（a )製得之硫酸，並以空氣處理彼，此等處理可連續且以任 一順序進行。 以H?〇2處理可確使存在步驟（a )製得之硫酸中之 雜質有機化合物被氧化破壞，此等雜質係由工業B F 3水合 物產生。所使用之化學反應爲： C 有 *+2H2〇2—C〇2+2H2〇 ( 2 ) 其中Ce«表示該有機雜質，亦指^有機來源碳# 。 以H2〇2處理之優點係其產生無色HaSO.:。 所使用之過氧化氫數量限制寬鬆。爲進行經濟處理， 以下列方式測定過氧化氫數量爲佳：使用總有機碳分析器 本紙張尺度適用tHS家摞準（CNS)A4規格（210x297公« ) <請先閱讀背面之注意事項再填寫本頁) 裝 -------------f 經濟部智慧財產局員工消费合作社印製 雄 Ο ' Α7 Β7 五、發明說明（5 ) 定量測定存在步驟（a )所使用工業B ?3水合物中之有機 來源碳之重量。以莫耳數表示H2〇2數量，其介於以此方 式測定之有機來源碳莫耳當量數之4與2 0 0倍，介於5 與2 0倍爲佳。 通常使用呈水溶液形式之過氧化氫，其濃度介於3與 70%，介於10與70%爲佳。 在介於8 0與1 1 5t：溫度下以H2〇2進行處理，該 溫度介於1 0 5與1 1 0 t爲佳。 本發明方法步驟（.c )之空氣處理可以大致去除所有 溶解於硫酸中之三氟化硼，較佳目的係使降低其B F 3含量 ，使之少於5 0 p pm。此處理通常係以沖洗方式進行》 如此可將釋出之B F3良好地吸收在水中，製得B F3水合 物，此可選擇性再循環至本發明方法步驟（a )。 本發明方法可以連續或分批操作。 若分批操作，可於第一反應器中進行本發明方法之步 驟（a)。可於兩個不同反應器或同一反應器中進行 Η 2 0 2處理與空氣沖洗作用，該反應或此等反應器視情況 可爲步驟（a)中所使用者。可先以Η2〇2進行處理，然 後空氣沖洗，或者反之亦可。 該方法連續操作爲佳，當連續操作時，使用三個依序 相連之反應器爲佳，第一反應器用以進行發煙硫酸與工業 B F 3水合物’並於頂部收集氣態B F 3，其他兩個反應器 係用以連續且以任一順序進行Η 2 0 2處理與空氣沖洗。 該第一反應器係一攪拌反應器爲佳*其中以將溢流導 本紙張尺度適用t困國家標準（CNS)A4規格（210 X 297公釐） (锖先閲讀背面之注意事項再填窝本I) 裝--------訂------|!嫂 經濟部智慧財產局員工消费合作杜印製 -8- 4 β〇4〇9 A7 B7 五、發明說明（6 ) 入第二反應器之方式使該反應介質（H2S 〇4 1 0 0%) 保持恒定水準。 下列實施例說明本發明但是不限制本發明。除非另有 所述1否則該百分比均以重量計。 實施例1. 使用包括兩個依序相連反應器之實例。第一反應器之 容量爲4 0 0毫升（2 0 0毫升容積係用於裝盛反應介質 )而且具有（4 -刮刀.）直徑爲4厘米之螺旋攪拌器；該 攪拌器頭之旋轉速度爲每分鐘5 0 0轉。此反應器具有一 個套管，其中有熱交換流體流過以逸散反應熱，並使溫度 保持介於104與107 °C。 連續稱出這兩種反應物-工業B F3A合物與6 5%發 煙硫酸，並導入反應器中，其包含最初裝塡量2 0 0毫升 1 0 0%碑酸。利用一個peristaiic栗供應工業B F 3水合 物，經由一個活塞型計量栗供應該發煙硫酸，經由兩個並 排之浸漬管進料反應介質。將反應器之溢流直接導入具有 與第一反應器相同特徵（容積、攪拌裝置等）之第二反應 器。該工業B F3水合物具有下列特徵： B F 3 =55 · 3 % Η 2 0 = 4 4 · 7 % 密度 =1.505 而且其有機碳含量係每公斤工業B Fa水合物包含8 3毫克 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） -9- <請先閱婧背面之注意事項再填寫本頁)Q On the other hand, industrial B F3 intended for catalytic applications must be free of organic matter and carbon dioxide. ≫ The industrial product must contain less than 10 mg of organic carbon and less than 5 mg of CO2 per kg of B F3. A method has now been found which can prepare boron trifluoride and sulfuric acid corresponding to industrial specifications from industrial B F3 hydrate and oleum. The special advantage of this method is that it does not generate waste and does not require the use of activated carbon. The method of the present invention comprises the following continuous steps: (a) reacting oleum with industrial B F3 hydrate, (b) collecting the released gaseous industrial B F3, and (c) treating the sulfuric acid of step (a) with hydrogen peroxide By-products and treated with air. B F3 hydrate is a dihydrate of the general formula B Fs · 2 H2 0 and is used in the form of an aqueous composition called industrial B F 3 hydrate according to the method of the present invention. The composition mainly includes a mixture of water and dihydrate and the above impurities. The gaseous BF 3 is usually absorbed in water, then it is used in various polymerization methods (poly-olefinic hydrocarbons, petroleum resins, etc.), and the polymer prepared from the polymerization is washed with water to wash the composition Thing. It can also be self-hydrolyzed by the use of BF 3 complexes, such as, for example, BBa ^ O (C2H5) 2. The B F3 content of the industrial B compound to be treated is very limited, but in terms of easy upgrading, the use concentration is between 35 and 65 · 3% of industrial 8 1 ^ 3 hydrate is preferred, and between 4 7 and 6 5.3% is more preferred (expressed as B F3 weight per 100 grams of water-containing composition). Unless otherwise specified, this paper size is applicable to the standard 0 (CNS) A4 (210 X 297 mm) -5- — — III — .----- * III ί Order-—I —III — * blowing (Please read the precautions on the back before filling in this page) 4 6〇〇〇7 A7 B7 V. Description of the invention (3), otherwise the percentages shown in this article are weight percentages. It can also be per BF 3 per mole The Mohr number of water X (relative to anhydrous molecules, that is, molecules without complexing water) represents the BF3 content of the industrial B F3 hydrate. Therefore, the above-mentioned range of B F3 weight content equivalent to X 値 is a broad range between about 0 and 5, the preferred range is between about 0 and 2.2. Therefore, the mixture of water and dihydrate present in industrial BF3 hydrate can be defined as BF3 · 2H2O + xH2O. If necessary, such as patent EP 3 6 As described in 4 8 1 5, the method for achieving this B F3 content is to remove water under vacuum and dilute the B hydrate concentratedly: the concentrated hydrate discharged from the bottom of the tower contains traces of heavy organic matter (organic carbon content: from about 10 To 1000 ppm). The fuming sulfuric acid used in the method of the present invention is a sulfuric anhydride S 03 in sulfuric acid. The solution, the content of S 〇3 of this solution is between 5 and 6 5%, preferably between 10 and 65. This content can also dissolve 1 Moore S 〇3 H2 S 〇4. Molar number y said Therefore, the y 含量 corresponding to the above-mentioned weight range of S03 is preferably between 0.44 and 15.5, and preferably between 0.44 and 7.4. The oleum can be expressed as: S03 + y ξ S 0 4 ° From industrial BF3 hydrate and oleum (the preparation of boron trifluoride in steps is equivalent to the following reaction: (BF) · 2H2〇 + xH2〇) + (2 + x) [S〇3 + yH2S〇4 ] — BF3 + (2 + x. + 2y + xy) HiSOt ⑴ (Jing first read the notes on the back before filling out this page) Binding ---- Order * ------ 1-^ 'Intellectual Property of the Ministry of Economic Affairs The staff of the Bureau eliminated and cooperated with the printed paper. The paper size is applicable to the AA standard (CNS) A4 specification < 210 X 297 mm) -6-A7 B7 V. Description of the invention (4) where X and y are as described above. The method of selecting the content of oleum and industrial BF 3 hydrate reacted in step (a) of the method of the present invention is the amount of oleum (expressed as S mol) divided by the amount of industrial hydrate (as anhydrous or composite water) The total number of moles indicated) is between 0.5 and 1.5, preferably close to 1. "The reaction in step (a) is usually performed at a temperature between 75 and 110 ° C, between 100 and 110 ° C. Better. According to step (b) of the method of the present invention, the gaseous boron trifluoride released from the reaction and collected is usually located at the top of the reaction, which does not contain nitrogen or carbon dioxide. It has all the characteristics of a commercially available product and can be processed so as to be supplied in a general manner, for example via compression. In step (c) of the method of the present invention, sulfuric acid produced in step (a) is treated with argon peroxide, and each is treated with air. These treatments can be performed continuously and in any order. Treatment with H? O2 can confirm that the organic compounds of impurities in the sulfuric acid obtained in step (a) are oxidized and destroyed, and these impurities are produced by industrial B F 3 hydrate. The chemical reaction used is: C has * + 2H2〇2—C〇2 + 2H2〇 (2) where Ce «represents the organic impurity, and also refers to ^ organic source carbon #. The advantage of treating with H2O2 is that it produces colorless HaSO.:. The restrictions on the amount of hydrogen peroxide used are relaxed. For economical treatment, it is better to measure the amount of hydrogen peroxide in the following way: Use total organic carbon analyzer This paper size is applicable to tHS furniture standard (CNS) A4 specification (210x297 male «) < Please read the precautions on the back before (Fill in this page) Install ------------- f Printed by the Consumers 'Cooperative of Intellectual Property Bureau of the Ministry of Economic Affairs 〇' Α7 Β7 V. Description of the invention (5) Existing step (a) used for quantitative determination Weight of organic-derived carbon in Industrial B-3 hydrate. Molar number represents the amount of H2O2, which is between 4 and 200 times, and preferably between 5 and 20 times the number of organic source carbon molar equivalents measured in this way. Hydrogen peroxide is usually used in the form of an aqueous solution, with a concentration between 3 and 70%, preferably between 10 and 70%. It is treated with H2O2 at a temperature between 80 and 115 t, and the temperature is preferably between 105 and 110 t. The air treatment in the method step (.c) of the present invention can substantially remove all boron trifluoride dissolved in sulfuric acid, and the preferred purpose is to reduce its B F 3 content to less than 50 p pm. This treatment is usually carried out in a rinsing mode, so that the released B F3 can be well absorbed in water to produce a B F3 hydrate, which can be selectively recycled to step (a) of the method of the present invention. The process according to the invention can be operated continuously or in batches. If operated in batches, step (a) of the process of the invention can be carried out in a first reactor. It can be carried out in two different reactors or in the same reactor. The Η 2 2 treatment and the air flushing effect, the reaction or these reactors may be the users in step (a) as the case may be. It can be treated with Η202, followed by air flushing, or vice versa. The continuous operation of this method is better. When the operation is continuous, it is better to use three reactors connected in sequence. The first reactor is used for fuming sulfuric acid and industrial BF 3 hydrate 'and collects gaseous BF 3 at the top. Each reactor is used to carry out the Η 2 2 treatment and the air flushing continuously and in any order. The first reactor is preferably an agitated reactor. Among them, the overflow guide is applied to the paper standard (CNS) A4 (210 X 297 mm) (锖 Please read the precautions on the back before filling the nest Book I) -------- Order ------ |! 嫂 Consumer cooperation with employees of the Intellectual Property Bureau of the Ministry of Economic Affairs Du printed -8-4 β〇4〇9 A7 B7 V. Description of the invention (6 The method of entering the second reactor keeps the reaction medium (H2S 0 4 100%) at a constant level. The following examples illustrate the invention without limiting it. The percentages are by weight unless otherwise stated. Example 1. Example using two reactors connected sequentially. The capacity of the first reactor is 400 ml (200 ml volume is used to hold the reaction medium) and has a (4-scraper.) Spiral agitator with a diameter of 4 cm; the rotation speed of the agitator head is 5000 revolutions per minute. This reactor has a sleeve in which a heat exchange fluid flows to dissipate the heat of reaction and keep the temperature between 104 and 107 ° C. These two reactants, the industrial B F3A complex and 65% oleum were successively weighed out and introduced into the reactor, which contained an initial loading of 200 ml of 100% benzoic acid. A peristaiic chestnut was used to supply industrial B F 3 hydrate, the fuming sulfuric acid was supplied through a piston-type metering chestnut, and the reaction medium was fed through two side-by-side dipping tubes. The overflow from the reactor was directly introduced into a second reactor having the same characteristics (volume, stirring device, etc.) as the first reactor. The industrial B F3 hydrate has the following characteristics: BF 3 = 55 · 3% Η 2 0 = 4 4 · 7% Density = 1.505 and its organic carbon content is 8 3 mg per kg of industrial B Fa hydrate. Applicable to this paper scale China National Standard (CNS) A4 Specification (210 X 297 mm) -9- < Please read the notes on the back of Jing before filling this page)
裝----- u n an n I 經濟部智慧財產局S工消费合作杜印製Equipment ----- u n an n I Intellectual Property Bureau of the Ministry of Economy
4 6 0 4、.J A7 B7 五、發明說明（7 ) 所使用之發煙硫酸分析物爲6 5%S〇3與3 5% (請先閱讀背面之注意事項再填寫本頁) H2 S 0.1。該工業B F a水合物之進料速率爲2 1 4克/ 小時，發煙硫酸之進料速率爲6 6 9克/小時，（發煙硫 酸中S〇3之莫耳數）對（無水或複合物水b f 3水合物莫 耳數）比相當於1。溢流之硫酸流速爲7 7 3克/小時。 在第一反應器中以過氧化氫處理來自第—反應器之硫 酸；H2O2之用量爲3 . 1克/小時1〇%H2〇2，該反 應介質溫度保持低於1 0 4與1 0 7°C。 爲收集第二反應器.硫酸中之溶解BF3 (1 . 5質量％ )*對該酸進行空氣沖洗。該經處理硫酸之BF3含量少於 5 0 p pm ’而存在沖洗空氣中之B F3吸附該塔的水中， 並以B F 3水溶液形式再循環。 以空氣沖洗B F 3之後，分析該硫酸爲9 9 . 9% H2 S 〇4 ’並將來自第二反應器溢流之硫酸冷卻至室溫。 經濟部智慧財產局負工消f合作社印製 此裝置連續操作7小時=將釋出之B F 3收集在第一反 應器頂部水阱（容量5升），並利用一磁性棒攬拌。分析 水中之B F3，測量其有機碳與無機碳（C 〇2氣）之含量 。多於9 0%之B F3 (最初呈B ?3水合物形式）係以 B F3氣體形式收集，其包含少於5毫克有機碳/公斤 B F 3氣體。未測得微量二氧化碳（偵測限制：1毫克 C〇2 /公斤BF3氣體）。此BF3具有工業BF3氣體特 徵。 製得之硫酸包含少於1 0毫克之有機碳/公斤（偵測 限制）》此等級之硫酸無色因此容易銷售。 -* 10 - 本紙張尺度適用中國國家標準（CNS>A4規格（210 X 297公釐） ,^ 460409 A7 _____B7______ 五、發明說明（8 ) 實施例(對照實例） (锖先閱讀背面之沒意事項再填寫本頁) 使用與實施例1相同方法*但是不將過氧化氫導入第 二反應器。收集於第一反應器之B F 3具有工業B F 3氣體 特徵（有機碳含量少於5毫克/公斤B F3，未測得微量 C〇2)，但是來自第二反應器之硫酸呈黑色，而且包含 20毫克有機碳/公斤H2S〇4)。 實施例3 (對照實例）- 使用具有下列特徵之工業B 水合物重複實施例2之 方法： B F 3 =47 . 7 % H a 0 -52 . 3 % 密度 =1 · 3 8 有機碳含量：6 2 0毫克/公斤工業B F3水合物》 經濟部智慧財產局貝Η消费合作社印製 該工業B F3水合物之進料速率爲1 8 8克/小時’發 煙硫酸之進料速率爲6 8 1克/小時第二反應器溢流之殘 留硫酸數量爲7 8 4克/小時。沖洗該硫酸之前’其佔 BF3質量1 . 3%。空氣沖洗該BF3之後’該硫酸分析 爲 98 4%923〇4與1 . 6%H2〇。 將釋出之B F 3收集在第一反應器頂部水阱’分析水中 之B F3，測量其有機碳與無機碳（C〇2氣）之含量：其 含量係每公斤B F3中少於1 0毫克。 本紙張尺度適用中國國家標準（CNS>A4規格（210 X 297公釐） -11- ^'M46〇4d^ A7 ___B7__ 五、發明說明（9 ) 在第二反應器溢流收集得之硫酸中每公斤硫酸包含 1 5 5毫克有機碳。其呈深棕色，因此無法銷售。 (請先閱讀背面之注意事項再填寫本頁) 實施例4 (對照實例） 使用具有下列特徵之工業B F3水合物重複實施例3之 方法： B F 3 =53-5% Η 2 0 = 4 6 · 5 % 密度 =.1.47 有機碳含量：780毫克/公斤工業3?3水合物。 反應器中B F3水合物之進料速率爲2 1 0克/小時， 發煙硫酸之進料速率爲667克/小時。以4.1克/小 時之進料速率將7 0 %過氧化氫導入同一反應器中。 該反應器溢流處之硫酸流爲7 8 4克/小時。該酸包 含1 . 1%BF3。沖洗之後，該硫酸分析呈97 . 2% H 2 S 0 4 與 2 . 8 % 水。 經濟部智慧財產局貝Η消费合作社印製 來自反應頂部之B F3*每公斤B F3包含5 3 0 0毫 克C 〇2，使其不適於工業用途》該硫酸中每公斤酸之有機 碳含量少於1 0毫克。 實施例5 使用與實施例4所述相同操作技術，但是將過氧化氫 導入第二反應器，並以相同速率4.1克/小時導入70 -12- 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） H.: .1， A7 _B7 五、發明說明（1〇 ) % Η 2 〇 2。 第一反應頂部之B F3具有工業B Fa水合物（有機碳 含量少於5毫克/公斤BF3，未測得微量C〇2)。來自 第二反應器之硫酸呈無色，其中每公斤酸包含少於1 0毫 克有機碳，因此可以應用於工業上。 (請先閱讀背面之沒意事項再填寫本頁) 經濟部智慧財產局貝工消費合作社印製 本紙張尺度適用中0國家摞準（CNS)A4規格（210 X 297公釐） -13-4 6 0 4. J. A7 B7 V. Description of the Invention (7) The oleum analytes used are 6 5% S0 3 and 3 5% (Please read the precautions on the back before filling this page) H2 S 0.1. The feed rate of the industrial BF a hydrate is 214 g / h, and the feed rate of fuming sulfuric acid is 6.9 g / h. (Moore number of S03 in fuming sulfuric acid) The complex water bf 3 hydrate mole number) ratio is equivalent to one. The overflow sulfuric acid flow rate was 7 73 g / h. The sulfuric acid from the first reactor is treated with hydrogen peroxide in the first reactor; the amount of H2O2 is 3.1 g / h 10% H2O2, and the temperature of the reaction medium is kept below 104 and 107 ° C. To collect the second reactor, dissolved BF3 (1.5% by mass) in sulfuric acid * The acid was air flushed. The BF3 content of the treated sulfuric acid is less than 50 p pm ′ and the B F3 present in the flushing air adsorbs the water in the tower and is recycled as an aqueous B F 3 solution. After flushing B F 3 with air, the sulfuric acid was analyzed to be 99.9% H2S04 and the sulfuric acid from the overflow from the second reactor was cooled to room temperature. Printed by the Ministry of Economic Affairs, Intellectual Property Bureau, Consumers Cooperative This device is continuously operated for 7 hours = the released B F 3 is collected in a water trap (capacity 5 liters) on the top of the first reactor, and mixed with a magnetic rod. Analyze B F3 in water and measure the content of organic carbon and inorganic carbon (C02 gas). More than 90% of B F3 (originally in the form of B 3 hydrate) was collected as B F3 gas, which contained less than 5 mg of organic carbon per kg of B F 3 gas. No trace carbon dioxide was detected (detection limit: 1 mg CO 2 / kg BF3 gas). This BF3 has industrial BF3 gas characteristics. The sulfuric acid produced contains less than 10 mg of organic carbon per kg (detection limit). This grade of sulfuric acid is colorless and therefore easy to sell. -* 10-This paper size applies to Chinese national standard (CNS > A4 specification (210 X 297 mm), ^ 409409 A7 _____B7______ V. Description of the invention (8) Examples (comparative examples) (锖 Read the unintended items on the back first) (Fill in this page again) Use the same method as in Example 1 * but do not introduce hydrogen peroxide into the second reactor. BF 3 collected in the first reactor has the characteristics of industrial BF 3 gas (organic carbon content is less than 5 mg / kg B F3, no trace of CO 2) was detected, but the sulfuric acid from the second reactor was black and contained 20 mg of organic carbon / kg of H 2 SO 4). Example 3 (comparative example)-The method of Example 2 was repeated using Industrial B hydrate having the following characteristics: BF 3 = 47.7% H a 0 -52. 3% Density = 1 · 3 8 Organic carbon content: 6 20 mg / kg Industrial B F3 Hydrate "Printed by the Intellectual Property Bureau of the Ministry of Economic Affairs, Behr Consumer Cooperative, the feed rate of the industrial B F3 hydrate is 1.8 8 g / h. The feed rate of fuming sulfuric acid is 6 8 The amount of residual sulfuric acid in the overflow from the second reactor at 1 g / h was 7.4 g / h. Before the sulfuric acid was washed, it accounted for 1.3% of the BF3 mass. After the BF3 was flushed by air, the sulfuric acid analysis was 98 4% 92304 and 1.6% H2O. Collect the released BF 3 in the water trap 'analysis water B F3 at the top of the first reactor, and measure the content of organic carbon and inorganic carbon (C02 gas): its content is less than 10 per kg of B F3 Mg. This paper size applies Chinese national standard (CNS > A4 specification (210 X 297 mm) -11- ^ 'M46〇4d ^ A7 ___B7__ V. Description of the invention (9) Each of the sulfuric acid collected in the overflow of the second reactor Kg sulfuric acid contains 155 mg of organic carbon. It is dark brown and cannot be sold. (Please read the precautions on the back before filling out this page) Example 4 (Comparative Example) Repeated using Industrial B F3 hydrate with the following characteristics Method of Example 3: BF 3 = 53-5% Η 2 0 = 4 6 · 5% Density = .1.47 Organic carbon content: 780 mg / kg industrial 3-3 hydrate. B F3 hydrate in the reactor The feed rate was 210 g / h, and the feed rate of oleum was 667 g / h. 70% hydrogen peroxide was introduced into the same reactor at a feed rate of 4.1 g / h. The reactor overflowed The sulfuric acid flow was 7.4 g / hr. The acid contained 1.1% BF3. After washing, the sulfuric acid analysis showed 97.2% H 2 S 0 4 and 2.8% water. ΗConsumer cooperative prints B F3 from the top of the reaction * 5 kg mg C 2 per kg B F3, making it unsuitable for industrial use The organic carbon content per kilogram of acid in the sulfuric acid is less than 10 mg. Example 5 The same operating technique as described in Example 4 was used, but hydrogen peroxide was introduced into the second reactor and the rate was 4.1 g / Hours of introduction 70 -12- This paper size is applicable to Chinese National Standard (CNS) A4 (210 X 297 mm) H .: .1, A7 _B7 V. Description of the invention (1〇)% Η 2 02. First reaction B F3 at the top has industrial B Fa hydrate (organic carbon content is less than 5 mg / kg BF3, no trace C02 is measured). The sulfuric acid from the second reactor is colorless, where each kg of acid contains less than 10 Milligrams of organic carbon, so it can be used in industry. (Please read the unintentional matter on the back before filling out this page.) Printed by the Intellectual Property Bureau of the Ministry of Economic Affairs, Shellfish Consumer Cooperatives. (210 X 297 mm) -13-